CN101830505A - Scandium oxide-stabilizing zirconia powder and preparation method thereof - Google Patents
Scandium oxide-stabilizing zirconia powder and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a scandium oxide-stabilizing zirconia powder and a preparation method thereof. The scandium oxide-stabilizing zirconia powder comprises zirconium oxychloride as precursor mother salt, one or more third elements of aluminum oxide, cerium oxide and bismuth oxide and a doping system, wherein the doping quantity of the scandium oxide is 8 mol%, and the total doping quantity of the aluminum oxide, the cerium oxide and the bismuth oxide is 0-7 wt%. The preparation method comprises the steps of water washing, filtration, drying, calcinations and powder surface dry and wet modification as well as constant-pressure hydrolysis reaction and low-pressure hydro-thermal reaction, wherein the constant-pressure hydrolysis reaction and low-pressure hydro-thermal reaction are carried out by the steps of: firstly carrying out constant-pressure hydrolysis on a water solution of the precursor mother salt ZrOCl2 (ScCl3) in a reactor, and then carrying out hydro-thermal treatment on hydrolysis liquid at the temperature less than 150 DEG C and the pressure of 0.3-0.5 MPa. The scandium oxide-stabilizing zirconia powder has the characteristics of small grain size, centralized size distribution, high sintering activity, lower specific surface area, suitability for the traditional casting process of a SOFC (Solid Oxide Fuel Cell) and high conductivity and strength index, and the preparation method has the advantages of simple and safe production process, lower cost, low requirement for equipment and easy realization of industrial big production.
Description
Technical field
The present invention relates to a kind of scandium oxide-stabilizing zirconia powder and preparation method thereof.
Background technology
Scandium oxide-stabilizing zirconia (Scandia Stabilized Zirconia, ScSZ) powder, has the characteristic that particle diameter is little, size-grade distribution is concentrated, sintering activity is high, specific surface area is lower, can be widely used in the existing flow casting molding method of SOFC (SolidOxide Full Cells, Solid Oxide Fuel Cell) ionogen substrate.
Under the overall situation of energy scarcity, as a kind of clear energy sources of new and effective green, SOFC has vast market and application prospect, and therefore, the research of SOFC has caused the extensive concern of countries in the world.Developed country such as American-European-Japanese has realized laboratory small power commercialization, is just concentrating strength at present, quickens to advance commercialization, and each risk investment company also is numerous and confused investment.And at home, owing to start late and external implementation blockade on new techniques, the SOFC state of the art of China also is in developmental stage at present.
One of core component of SOFC is an electrolyte.At present, most SOFC are solid electrolyte with the adulterated zirconium white of 6-10mol% yttrium oxide (YSZ) all, but its specific conductivity is lower, the mechanical property performance is general, has restricted further developing of SOFC.Therefore, must seek to have the novel material of high conductivity.At ZrO
2In the system, because the influence of dot matrix stress and steric effect replaces Zr
4+Cation radius and Zr
4+Radius is approaching more, and specific conductivity is high more.According to pertinent data, at stable ZrO
2In the system, Sc
2O
3Stable ZrO
2Binary system has higher specific conductivity.
Lee, employing glycine-nitrate process such as D. have prepared the stable Zirconium oxide powder of 8mol% scandium, and this powder forms pure cube of phase or quadrangle at 1600 ℃ of following sintering 6h, its conductivity=0.15S/cm (800 ℃).Employing coprecipitation methods such as peace triumph have been synthesized scandium oxide-stabilizing zirconia (9mol%Sc
2O
3, ScSZ) powder, use heat dilatometric analysis instrument has been studied the sintering characteristic of ScSZ powder, the microtexture of sintered specimen that adopted scanning electron microscopic observation; And to have prepared with ScSZ be ionogen, Cu-CeO
2-ScSZ is that anode, ScSZ-LSM are the anode-supported fuel cell of negative electrode, in the time of 700 ℃, is fuel with hydrogen, butane and methane directly, and the battery peak power output density that records is respectively 280mW/cm
2, 142mW/cm
2And 120mW/cm
2Mizutani Yasunobu etc. are raw material with scandium powder, zirconium powder end and nitric acid, adopt coprecipitation method and sol-gel method to prepare the ScSZ powder respectively, this powder need could finally be made the electrode slice goods through isostatic pressing and the severe condition of burning till under 1500～1700 ℃ high temperature.Y.Mizutani etc. are with ZrO (NO
3)
22H
2O and purity are 99.9% Sc
2O
3Be raw material, adopt sol-gel method to prepare the 8ScSZ powder, (pressure is 2000Kg/cm to this powder through 1600-1700 ℃ of hot pressed sintering
2) record conductivity=0.38S/cm (1000 ℃), bending strength K behind the 5-15h
f=275MPa; In addition, the author has added Al in this system
2O
3To improve its bending strength, add 20wt%Al
2O
38ScSZ-20wt%Al
2O
3The bending strength of compound system can be brought up to 414MPa, but the specific conductivity of this moment has dropped to 0.14S/cm.
To sum up, the existing method for preparing material, as sol-gel method, propylhomoserin-nitrate process is difficult to form suitability for industrialized production, and there is hard aggregation in the prepared powder of coprecipitation method and the defective such as inhomogeneous of mixing, and the prepared ScSZ powder of aforesaid method all exists firing temperature height, shortcoming that soaking time is long.So far, the compatibling problem of both unresolved specific conductivity of ScSZ electrolyte and intensity index does not find the low cost process and the method that are fit to suitability for industrialized production yet, thereby has delayed to advance the commercial applications process of SOFC.
Summary of the invention
Its purpose of the present invention just is to provide a kind of scandium oxide-stabilizing zirconia powder and preparation method thereof, have that particle diameter is little, size-grade distribution is concentrated, sintering activity is high, specific surface area is lower, the existing casting molding processes of SOFC can be fit to, and the characteristics of high conductivity high strength index can be taken into account simultaneously, production technique is simple, safety, cost is lower, and not high to equipment requirements, be easy to realize industrialized production.
The technical scheme that realizes above-mentioned purpose and take,
A kind of scandium oxide-stabilizing zirconia powder, comprise the female salt zirconium oxychloride of presoma, also comprise one or more the 3rd constituent element and doping systems among aluminum oxide, cerium oxide, the bismuth oxide, wherein the Scium trioxide doping accounts for 8mol%, and the doping total amount of aluminum oxide, cerium oxide, bismuth oxide accounts for 0-7wt%.
A kind of scandium oxide-stabilizing zirconia powder preparation method, comprise washing, filter, dry, calcining, powder dry method, wet method surface modification treatment, also comprise ordinary-pressure hydrolysis reaction and low-pressure water thermal response, at first the aqueous solution of the female salt ZrOCl2 of presoma (ScCl3) is carried out ordinary-pressure hydrolysis in reactor and handle, then hydrolyzed solution is carried out hydrothermal treatment consists under＜150 ℃ temperature and 0.3-0.5MPa pressure.
Compared with prior art the present invention has the following advantages.
1, the present invention " ordinary-pressure hydrolysis--low pressure hydro-thermal " new technology of combined has been avoided the harsh working condition of hydrothermal method High Temperature High Pressure, and production technique is simple, safety, and cost is lower, and not high to equipment requirements, is easy to realize industrialized production.
2, powder of the present invention has solved the contradiction between sintering activity and the specific surface area---the lower (S of specific surface area
BET=11.2 ± 0.4m
2/ g), be suitable for very much the existing flow casting molding method of SOFC; The sintering activity height can save production cost in lower temperature (1350 ℃) and normal pressure-sintered down than short soaking time (3h).
3, powder of the present invention can be taken into account the requirement of high conductivity high strength index simultaneously, conductivity＞0.28S/cm (1000 ℃), 3 folding strength K
f＞500MPa.
4, powder of the present invention consists of 8ScSZ, compares with commercially available 10ScSZ powder, and cost is low---and the material cost of ScSZ powder is mainly Sc
2O
3Cost, by present calculation of price, the Sc that every minimizing 1% is formed
2O
3, about 100 yuan/kilogram of costs just can save material.
5, powder of the present invention has that particle diameter is little, size-grade distribution is concentrated, sintering activity is high, specific surface area is lower, the existing casting molding processes of SOFC can be fit to, and the characteristics of high conductivity high strength index can be taken into account simultaneously, its production technique is simple, safety, cost is lower, and not high to equipment requirements, be easy to realize industrialized production.
Description of drawings
The invention will be further described below in conjunction with accompanying drawing.
Accompanying drawing is the process flow diagram of preparation 8ScSZ powder.
Embodiment
Comprise the female salt zirconium oxychloride of presoma, also comprise one or more the 3rd constituent element and doping systems among aluminum oxide, cerium oxide, the bismuth oxide, wherein the Scium trioxide doping accounts for 8mol%, and the doping total amount of aluminum oxide, cerium oxide, bismuth oxide accounts for 0-7wt%.
Its size of described powder is 60-80nm, aggregated particle size size D
50＜0.50 μ m, S
BET=11.2 ± 0.4m
2/ g can be normal pressure-sintered under 1350 ℃-3h condition.
The preparation method, comprise washing, filter, dry, calcining, powder dry method, wet method surface modification treatment, also comprise ordinary-pressure hydrolysis reaction and low-pressure water thermal response, at first the aqueous solution of the female salt ZrOCl2 of presoma (ScCl3) is carried out ordinary-pressure hydrolysis in reactor and handle, then hydrolyzed solution is carried out hydrothermal treatment consists under＜150 ℃ temperature and 0.3-0.5MPa pressure.
Add being compounded with organic additive in described ordinary-pressure hydrolysis reaction and the low-pressure water thermal response, add mineralizer in the described low-pressure water thermal response.
Find that after deliberation crystal boundary state and grain size, cerium oxide that the grain size of the crystalline phase that how much influences Zirconium powder of Scium trioxide doping and sintered compact, intensity that aluminum oxide influences goods and sintering character, bismuth oxide influence sintered compact influence the aging resistance of goods, and then influence use propertieies such as the specific conductivity of SOFC electrode slice of Zirconium powder institute moulding and intensity.
After deliberation, finally made the low-cost main body prescription of 8mol% Scium trioxide doped zirconia, and in this main body prescription doped aluminium, cerium oxide and bismuth oxide, finally prepared powder with the object of the invention excellent specific property; In addition, provide a kind of method of suitable industrialized production: by the concentration of the female salts solution of control presoma, compactedness, hydrolysis temperature and hydrolysis time, and add the organic additive that is compounded with of appropriate system, accurately control its add-on, at first the aqueous solution with the female salt ZrOCl2 of presoma (ScCl3) carries out the ordinary-pressure hydrolysis processing in reactor, then by choosing the mineralizer of suitable species, and accurately control the optimum amount of mineralizer, and the reactor (length-to-diameter ratio that comprises reactor by the utilization structure appropriate design, alr mode and speed, body material, the type of cooling etc.), hydrolyzed solution is carried out hydrothermal treatment consists under lower temperature (＜150 ℃) and pressure (0.3-0.5MPa), i.e. " ordinary-pressure hydrolysis--low pressure hydro-thermal " method new technology of combined; Thereby finished the present invention.
A kind of scandium oxide-stabilizing zirconia powder, its particle diameter is little, size-grade distribution is concentrated, specific surface area is lower, sintering activity is high, the SOFC electrode slice of making of this powder can be taken into account the requirement of high conductivity and high strength index simultaneously, satisfies the strict demand of SOFC ionogen to material fully.
Scandium oxide-stabilizing zirconia powder is to mix through one or more the 3rd constituent elements among aluminum oxide, cerium oxide, the bismuth oxide to optimize; Wherein the Scium trioxide doping accounts for 8mol%, and the doping total amount of aluminum oxide, cerium oxide, bismuth oxide accounts for 0-7wt%.
Scandium oxide-stabilizing zirconia powder, its size is 60-80nm, aggregated particle size size D
50＜0.50 μ m, S
BET=11.2 ± 0.4m
2/ g can be normal pressure-sintered under 1350 ℃-3h condition, preferably resolves the contradiction between specific surface area and the sintering activity.
Described powder, flow casting molding SOFC ionogen substrate, under the condition of normal pressure behind the sintering, its conductivity＞0.28S/cm (1000 ℃), 3 folding strength K
f＞500MPa.
Described powder, be to utilize " ordinary-pressure hydrolysis--low pressure hydro-thermal " method to produce, captured the powder that under the single method condition, prepares or have hard aggregation, doping is inhomogeneous and firing temperature is high, or the harsh working condition of High Temperature High Pressure, the big production technology difficult problem of preparation difficulty, can be under the working condition of safety, produce high conductivity, high strength cheaply, easily disperse, easily densification sintering less or soft-agglomerated ScSZ powder.
Described " ordinary-pressure hydrolysis--low pressure hydro-thermal " production method, at first the aqueous solution with the female salt ZrOCl2 of presoma (ScCl3) carries out the ordinary-pressure hydrolysis processing in reactor, then hydrolyzed solution is carried out hydrothermal treatment consists under lower temperature (＜150 ℃) and pressure (0.3-0.5MPa).
Embodiment
Further specify embodiment with following indefiniteness embodiment.
Embodiment 1:
In the reactor that designs in advance, prepare the female salt zirconyl chloride solution of certain density presoma, proportioning according to 8mol% adds Scium trioxide, heating and stirring make its dissolving, then this solution for preparing longer for some time of heating, add the mineralizer hydro-thermal again, through washing, suction filtration, oven dry calcining, promptly get powder of the present invention at last.
Embodiment 2:
In the reactor that designs in advance, prepare the female salt zirconyl chloride solution of certain density presoma, add Scium trioxide according to the proportioning of 8mol%, and add cerium oxide according to the proportioning of 0.5wt%, other conditions are with embodiment 1.
Embodiment 3:
" cerium oxide of 0.5wt% " among the embodiment 2 is changed to " aluminum oxide of 0.5wt% ", and all the other conditions are with embodiment 2.
Embodiment 4:
" cerium oxide of 0.5wt% " among the embodiment 2 is changed to " bismuth oxide of 0.5wt% ", and all the other conditions are with embodiment 2.
Embodiment 5:
In the reactor that designs in advance, prepare the female salt zirconyl chloride solution of certain density presoma, add the proportioning adding cerium oxide of Scium trioxide, 0.5wt%, the proportioning adding aluminum oxide of 0.5wt%, the proportioning adding bismuth oxide of 0.5wt% according to the proportioning of 8mol%, other conditions are with embodiment 1.
Embodiment 6:
Regulate the add-on of cerium oxide, aluminum oxide, bismuth oxide during batching, all the other conditions are with embodiment 5.
Embodiment 7:
Regulate the add-on of Scium trioxide during batching, all the other conditions are with embodiment 5.
Claims (4)
1. scandium oxide-stabilizing zirconia powder, comprise the female salt zirconium oxychloride of presoma, it is characterized in that, also comprise one or more the 3rd constituent element and doping systems among aluminum oxide, cerium oxide, the bismuth oxide, wherein the Scium trioxide doping accounts for 8mol%, and the doping total amount of aluminum oxide, cerium oxide, bismuth oxide accounts for 0-7wt%.
2. a kind of scandium oxide-stabilizing zirconia powder according to claim 1 is characterized in that, its size of described powder is 60-80nm, aggregated particle size size D
50＜0.50 μ m, S
BET=11.2 ± 0.4m
2/ g can be normal pressure-sintered under 1350 ℃-3h condition.
3. a kind of scandium oxide-stabilizing zirconia powder preparation method according to claim 1, comprise washing, filter, dry, calcining, powder dry method, wet method surface modification treatment, it is characterized in that, also comprise ordinary-pressure hydrolysis reaction and low-pressure water thermal response, at first the aqueous solution with the female salt ZrOCl2 of presoma (ScCl3) carries out the ordinary-pressure hydrolysis processing in reactor, then hydrolyzed solution is carried out hydrothermal treatment consists under＜150 ℃ temperature and 0.3-0.5MPa pressure.
4. a kind of scandium oxide-stabilizing zirconia powder preparation method according to claim 3 is characterized in that, adds being compounded with organic additive in described ordinary-pressure hydrolysis reaction and the low-pressure water thermal response, adds mineralizer in the described low-pressure water thermal response.
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Cited By (7)
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|---|---|---|---|---|
| CN102358826A (en) * | 2011-08-19 | 2012-02-22 | 永州皓志稀土材料有限公司 | Method for preparing aluminum-doped zirconium oxide compound polishing powder |
| CN103626492A (en) * | 2013-12-18 | 2014-03-12 | 江西赛瓷材料有限公司 | Scandia-stabilized zirconia powder for solid oxide fuel battery |
| CN104291816A (en) * | 2014-09-28 | 2015-01-21 | 江西赛瓷材料有限公司 | Powder material for preparing high-strength high-toughness yttrium stabilized tetragonal polycrystal zirconia ceramics and preparation method of powder material |
| CN111205088A (en) * | 2020-01-15 | 2020-05-29 | 中国恩菲工程技术有限公司 | Method for preparing scandia-stabilized zirconia powder by hydrothermal method and scandia-stabilized zirconia powder prepared by method |
| CN111233467A (en) * | 2020-01-15 | 2020-06-05 | 中国恩菲工程技术有限公司 | Oxide-doped scandium-zirconium powder and preparation method thereof |
| CN112164814A (en) * | 2020-09-29 | 2021-01-01 | 清华大学 | Preparation method of composite electrolyte layer of solid oxide fuel cell and solid oxide fuel cell |
| CN114133240A (en) * | 2021-11-30 | 2022-03-04 | 广东先导稀材股份有限公司 | Method for preparing scandium-cerium-ytterbium-doped zirconia superfine powder by hydrolysis-hydrothermal method |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102358826A (en) * | 2011-08-19 | 2012-02-22 | 永州皓志稀土材料有限公司 | Method for preparing aluminum-doped zirconium oxide compound polishing powder |
| CN102358826B (en) * | 2011-08-19 | 2013-08-07 | 湖南皓志新材料股份有限公司 | Method for preparing aluminum-doped zirconium oxide compound polishing powder |
| CN103626492A (en) * | 2013-12-18 | 2014-03-12 | 江西赛瓷材料有限公司 | Scandia-stabilized zirconia powder for solid oxide fuel battery |
| CN103626492B (en) * | 2013-12-18 | 2016-01-13 | 江西赛瓷材料有限公司 | For the Zirconium powder of the scandia stabilized in Solid Oxide Fuel Cell |
| CN104291816A (en) * | 2014-09-28 | 2015-01-21 | 江西赛瓷材料有限公司 | Powder material for preparing high-strength high-toughness yttrium stabilized tetragonal polycrystal zirconia ceramics and preparation method of powder material |
| CN111205088A (en) * | 2020-01-15 | 2020-05-29 | 中国恩菲工程技术有限公司 | Method for preparing scandia-stabilized zirconia powder by hydrothermal method and scandia-stabilized zirconia powder prepared by method |
| CN111233467A (en) * | 2020-01-15 | 2020-06-05 | 中国恩菲工程技术有限公司 | Oxide-doped scandium-zirconium powder and preparation method thereof |
| CN112164814A (en) * | 2020-09-29 | 2021-01-01 | 清华大学 | Preparation method of composite electrolyte layer of solid oxide fuel cell and solid oxide fuel cell |
| CN112164814B (en) * | 2020-09-29 | 2021-11-30 | 清华大学 | Preparation method of composite electrolyte layer of solid oxide fuel cell and solid oxide fuel cell |
| CN114133240A (en) * | 2021-11-30 | 2022-03-04 | 广东先导稀材股份有限公司 | Method for preparing scandium-cerium-ytterbium-doped zirconia superfine powder by hydrolysis-hydrothermal method |
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Application publication date: 20100915 |